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EP0633231B1 - Inorganic resins, process for their preparation and thermal protection articles - Google Patents

Inorganic resins, process for their preparation and thermal protection articles Download PDF

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Publication number
EP0633231B1
EP0633231B1 EP94401440A EP94401440A EP0633231B1 EP 0633231 B1 EP0633231 B1 EP 0633231B1 EP 94401440 A EP94401440 A EP 94401440A EP 94401440 A EP94401440 A EP 94401440A EP 0633231 B1 EP0633231 B1 EP 0633231B1
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EP
European Patent Office
Prior art keywords
inorganic
oxides
resin
resins
mixture
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94401440A
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German (de)
French (fr)
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EP0633231A1 (en
Inventor
Ludovic Neel
Claude L'hernault
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Societe Nationale des Poudres et Explosifs
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Societe Nationale des Poudres et Explosifs
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/92—Fire or heat protection feature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/92—Fire or heat protection feature
    • Y10S428/921—Fire or flameproofing

Definitions

  • the invention relates to new mineral resins based on alkaline boroaluminosilicates and process of preparation. It relates in particular to resins which harden at low temperatures and form mineral matrices with strong character endothermic when exposed to heat. They are therefore very useful for making thermal protection materials and in particular fire-resistant materials.
  • the invention relates to new resins alkaline boroaluminosilicate minerals quickly and easily obtained from compounds readily available with features constant and which allow to obtain materials stable over time, retaining their properties mechanical at temperatures above 200 ° C and useful as thermal protection materials.
  • X 2 0 represents Na 2 0, K 2 0 or a mixture of Na 2 0 and K 2 0, Li 2 0 and Na 2 0, Li 2 0 and K 2 0 or Li 2 0, Na 2 0 and K 2 0.
  • Alkali, silicon, aluminum oxides as well as the dissolved boron oxide combine to form the resin skeleton.
  • the resins form matrices which have good physical properties and mechanical and excellent endothermic character.
  • They can be used as protection against thermal stress as a structure freestanding or cladding.
  • One or more very diverse, organic fillers, mineral and / or metallic can be incorporated in resins before hardening.
  • the charges are usually in granular or fibrous form.
  • these are mineral substances.
  • the proportion of charges is at most 50% in volume relative to the total volume of the resin and charges.
  • sulfates especially those of calcium, magnesium, alumina, alumina hydrates, zinc oxide, borax and aluminosilicates.
  • resins may also be added such as pigments, adjuvants.
  • Another object of the present invention relates to the process for the preparation of these new resins.
  • a sufficiently fluid resin is thus obtained which can be cured immediately.
  • X 2 0 represents Na 2 0, K 2 0 or a mixture of Na 2 0 and K 2 0, Li 2 0 and Na 2 0, Li 2 0 and K 2 0 or Li 2 0, Na 2 0 and K 2 0.
  • the 1: 1 clays that make up the material first of the powder precursor are found in the trade. It is better that they are finely ground, and to get better reactivity, we preferably use those whose grains have a dimension less than 5 ⁇ m.
  • clay used is kaolin and preferably whose content in kaolinite is greater than 70%.
  • the clays must be amorphized in order to make reactive with the liquid precursor. Amorphization can be achieved by methods known.
  • a process that is well suited in the context of present invention is the heat treatment of clays preferably at a temperature between 600 ° C and 1100 ° C. The duration of treatment is a function of the temperature. At 700 ° C this duration is around of a few hours. At 1000 ° C a few seconds can suffice to obtain this amorphization.
  • Another way to achieve the amorphization of clays is to disperse them in strong and concentrated acids such than hydrochloric acid, sulfuric acid or acid nitric. We can perform successively several different amorphization treatments. When we perform the two previous treatments we prefer generally carry out the acid treatment before heat treatment.
  • Amorphization of clays can be ascertained by examining their spectra of X-ray diffraction in which should not appear neither the crystallization spectrum of the kaolinite, nor the spectra of the crystalline phases which are born at a temperature above 1100 ° C.
  • the liquid precursor is an aqueous solution which must contain, in the dissolved state, at least one element alkaline chosen from sodium, potassium and lithium, boron, which may be in a state of supersaturation, and possibly silicon.
  • the liquid precursor In order to obtain a stable liquid precursor it is firstly that all the constituents are well dissolved to form a solution. This dissolved state is also necessary for these constituents can form with the other constituents of the powder precursor the skeleton of the resin. Else apart the liquid precursor should not be too viscous so that it can be mixed with the precursor in powder and in order to obtain a sufficient resin fluid that can be molded or shaped and contain possibly charges or that can be used to impregnation. Preferably the viscosity of the precursor liquid is less than or equal to 30 poises.
  • Alkaline elements are usually introduced in the aqueous medium, by means of alkali hydroxides, Na0H, K0H and / or Li0H.
  • Boron is introduced by means of one of its forms and / or at least one of its compounds capable of dissolving in an aqueous and alkaline medium such as for example an oxide, salt, acid or hydroxide.
  • an aqueous and alkaline medium such as for example an oxide, salt, acid or hydroxide.
  • orthoboric acid is used.
  • the liquid precursor When it is desired to obtain a resin with a large proportion of boron, the liquid precursor must contain a very large quantity of this element and it is possible that for a ratio B 2 0 3 / Al 2 0 3 ⁇ 1.1, the solution contains a boron-based precipitate.
  • liquid precursor we prefer generally introduce into the water first the alkali hydroxide (s) then optionally the (s) silicate (s) and finally the boron compound (s). We can heat the mixture to promote good homogeneity.
  • the mixture of the liquid precursor and the precursor powder is carried out at room temperature, by example using a propeller mixer.
  • a homogeneous resin which can be poured or shaped which can be used to make objects by usual techniques including molding. This resin can then be cured without time rest is required.
  • the hardening results from the reaction that occurs and which can be akin to a hydrolysis-polycondensation reaction.
  • Curing can be done at a temperature between 0 ° and 150 ° C. Until room temperature, around 20 ° C, it is slow. We prefer to heat the resin to a temperature between 40 ° and 120 ° C.
  • the hardening time varies in depending on the formulation of the resin, the temperature and the heating mode used. Thanks to conventional heating by external heat input, some formulations cure in less than an hour at 80 ° C. By means of microwave heating a few seconds may be enough.
  • Curing is necessary in the presence of all the water present in the resin. We must therefore operate in the middle airtight or saturated with water.
  • resins according to the present invention are particularly useful as thermal protection materials and especially as a fire barrier. They can be molded in different forms and for example under form of panels. Tests performed with panels between 10 and 30 mm thick show that these materials are quite usable against thermal attacks such as particularly a gradual rise in temperature up to around 1200 ° or a thermal flash of ten minutes at 850 ° C.
  • a heat reflective element which can be consisting for example of a very thin layer of mica or flakes of an amorphous metal called "glass metallic "placed on the face (s) of the object and held by a glass mat impregnated with a resin uncharged mineral as described above which by hardening will bond.
  • the element reflector is placed on one or more faces to inside the mold which will receive the resin and will find related to the face (s) of the object after hardening of the whole.
  • the mixture is stirred and optionally heated in order to obtain good homogeneity.
  • the two precursors are mixed at room temperature by gradually incorporating the powder into the liquid solution in the proportions indicated by the following report:
  • L AT mass of liquid precursor mass of powder precursor
  • the resin and the fillers are vigorously mixed for about 10 minutes.
  • the resin alone or containing the fillers is then poured into a polyethylene box which is hermetically closed. We don't let it sit the whole, hardening is carried out immediately placing the box in an oven at 60 ° C. At this temperature the solidification of the loaded resin or no generally takes less than 15 hours. Some compositions cure in less than 5 hours.
  • Plates with dimensions 300 x 300 mm 2 and thickness 30 mm are produced which are subjected to thermal aggression according to ISO standard 834 on one side and the time required for the other side, rear, to be determined, reaches temperatures of 100 ° and 170 °.
  • the plates are obtained by introducing into a mold, the following compositions of resins, prepared as shown in the previous examples.
  • a conventional glass mat at 300 g / m 2 impregnated with one of the mineral resins of the invention having a rapid hardening is placed beforehand and on this mat a layer of approximately 0.2 mm d thickness consisting of metallic glass flakes with a length of 30mm, FIBRAFLEX sold by the company SEVA.
  • the mold is placed between the plates of a press whose temperature is 100 ° C. A pressure of 2 to 3 bars (0.2 to 0.3 MPa) is exerted in order to make the material flow and to fill the mold which is completely closed.
  • the plates are produced as before by introduction into a mold of the resinous compositions prepared as indicated in examples 1 to 8. Only the face placed on the side of the thermal attack and the sides optionally include a reflector constituted by a glass mat of 50 g / m 2 impregnated with a quick-hardening mineral resin according to the invention and with a layer of approximately 0.2 mm thick FIBRAFLEX flakes 15 mm long.
  • Resins are prepared containing as elements potassium and lithium alkalies, depending on mode procedure described in examples 1 to 8.
  • Lithium is introduced in the form of lithine (Li0H) powder.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Description

L'invention concerne de nouvelles résines minérales à base de boroaluminosilicates alcalins et leur procédé de préparation. Elle concerne en particulier des résines qui durcissent à basse température et forment des matrices minérales qui présentent un fort caractère endothermique lorsqu'elles sont exposées à la chaleur. Elles sont très utiles par conséquent pour fabriquer des matériaux de protection thermique et en particulier des matériaux coupe-feu.The invention relates to new mineral resins based on alkaline boroaluminosilicates and process of preparation. It relates in particular to resins which harden at low temperatures and form mineral matrices with strong character endothermic when exposed to heat. They are therefore very useful for making thermal protection materials and in particular fire-resistant materials.

Des résines minérales à base d'aluminosilicates alcalins ont été décrites notamment dans les demandes de brevet français FR 2 489 291 et 2 659 319 mais les matériaux fabriqués au moyen de ces résines qui sont dépourvues de bore présentent des propriétés mécaniques faibles dès que la température dépasse 200° C. Lorsqu'on les utilise comme barrières anti-feu, les gradients thermiques importants qui se produisent en leur sein provoquent dès 200° C des fissurations ou des déformations. On a aussi constaté que ces matériaux se modifiaient au cours du temps même à température ambiante. Des fissures apparaissent ainsi que des efflorescences en surface qui montrent que les résines ne sont pas stables chimiquement. D'autre part certains composés utilisés pour préparer les résines, tels que la silice thermique, ont des propriétés très variables suivant la source d'approvisionnement et il est alors difficile d'obtenir des résines présentant les mêmes caractéristiques au moyen des mêmes formulations. Un autre désavantage des résines de l'art antérieur est que leur durcissement ne peut être effectué immédiatement. Il est en effet nécessaire de les laisser au repos un certain temps, souvent quelques heures avant cette opération, ce qui allonge la durée d'obtention des matériaux.Mineral resins based on aluminosilicates alkaline have been described in particular in applications for French patent FR 2,489,291 and 2,659,319 but the materials made from these resins which are free of boron have mechanical properties low as soon as the temperature exceeds 200 ° C. When use them as fire barriers, gradients significant thermal that occurs within them cause from 200 ° C cracks or deformations. It has also been found that these materials changed over time even at temperature ambient. Cracks appear as well as surface efflorescence which shows that the resins are not chemically stable. On the other hand some compounds used to prepare resins, such as thermal silica, have very variable properties depending on the source of supply and then it's difficult to obtain resins having the same characteristics using the same formulations. A another disadvantage of the prior art resins is that their hardening cannot be carried out immediately. It is indeed necessary to leave them to rest for a some time, often a few hours before this operation, which lengthens the time required to obtain materials.

Il existait donc un besoin de nouvelles résines minérales qui ne possèdent pas les inconvénients des résines de l'art antérieur.There was therefore a need for new resins which do not have the disadvantages of prior art resins.

L'invention a pour objet de nouvelles résines minérales à base de boroaluminosilicates alcalins obtenues de façon simple et rapide à partir de composés facilement disponibles avec des caractéristiques constantes et qui permettent d'obtenir des matériaux stables dans le temps, conservant leurs propriétés mécaniques aux températures supérieures à 200° C et utiles comme matériaux de protection thermique.The invention relates to new resins alkaline boroaluminosilicate minerals quickly and easily obtained from compounds readily available with features constant and which allow to obtain materials stable over time, retaining their properties mechanical at temperatures above 200 ° C and useful as thermal protection materials.

Les nouvelles résines minérales selon l'invention comprennent, avant durcissement, les éléments minéraux à l'état réactif, le bore pouvant être aussi en état de sursaturation, dans les proportions suivantes exprimées par leur rapport molaire d'oxydes :

  • 2 ≤ Si02/Al203 ≤ 4
  • 1,3 ≤ X20/Al203 ≤ 3,8
  • 10 ≤ H20/Al203 ≤ 28
  • 0,5< B203/Al203 ≤ 2,0
    • X20 représentant un ou plusieurs oxydes alcalins choisis parmi Na20, K20 et Li20.The new mineral resins according to the invention comprise, before hardening, the mineral elements in the reactive state, the boron possibly also being in a supersaturation state, in the following proportions expressed by their molar ratio of oxides:
  • 2 ≤ Si0 2 / Al 2 0 3 ≤ 4
  • 1.3 ≤ X 2 0 / Al 2 0 3 ≤ 3.8
  • 10 ≤ H 2 0 / Al 2 0 3 ≤ 28
  • 0.5 <B 2 0 3 / Al 2 0 3 ≤ 2.0
    • X 2 0 representing one or more alkaline oxides chosen from Na 2 0, K 2 0 and Li 2 0.

    Avantageusement X20 représente Na20, K20 ou un mélange de Na20 et de K20, de Li20 et de Na20, de Li20 et de K20 ou de Li20, de Na20 et de K20.Advantageously X 2 0 represents Na 2 0, K 2 0 or a mixture of Na 2 0 and K 2 0, Li 2 0 and Na 2 0, Li 2 0 and K 2 0 or Li 2 0, Na 2 0 and K 2 0.

    Les résines préférées selon l'invention sont celles dont les rapports molaires des oxydes ont les valeurs suivantes :

  • 3,0 ≤ Si02/Al203 ≤ 3,8
  • 1,5 ≤ X20/Al203 ≤ 3,6
  • 13,0 ≤ H20/Al203 ≤ 19,5
  • 0,5< B203/Al203 ≤ 1,8
    • X20 représentant l'oxyde de potassium ou les valeurs suivantes :
  • 2,0 ≤ Si02/Al203 ≤ 3,9
  • 1,4 ≤ X20/Al203 ≤ 3,0
  • 10 ≤ H20/Al203 ≤ 28,0
  • 0,5< B203/Al203 ≤ 1,3
    •  X20 représentant l'oxyde de sodium ou un mélange d'oxyde de sodium et de potassium.The preferred resins according to the invention are those whose molar ratios of the oxides have the following values:
  • 3.0 ≤ Si0 2 / Al 2 0 3 ≤ 3.8
  • 1.5 ≤ X 2 0 / Al 2 0 3 ≤ 3.6
  • 13.0 ≤ H 2 0 / Al 2 0 3 ≤ 19.5
  • 0.5 <B 2 0 3 / Al 2 0 3 ≤ 1.8
    • X 2 0 representing potassium oxide or the following values:
  • 2.0 ≤ Si0 2 / Al 2 0 3 ≤ 3.9
  • 1.4 ≤ X 2 0 / Al 2 0 3 ≤ 3.0
  • 10 ≤ H 2 0 / Al 2 0 3 ≤ 28.0
  • 0.5 <B 2 0 3 / Al 2 0 3 ≤ 1.3
    • X 2 0 representing sodium oxide or a mixture of sodium and potassium oxide.

    Elles durcissent par réaction interne de type hydrolyse-polycondensation.They harden by internal type reaction hydrolysis-polycondensation.

    Les oxydes alcalins, de silicium, d'aluminium ainsi que l'oxyde de bore dissout s'associent pour former le squelette de la résine.Alkali, silicon, aluminum oxides as well as the dissolved boron oxide combine to form the resin skeleton.

    Une fois durcies les résines forment des matrices qui possèdent de bonnes propriétés physiques et mécaniques et un excellent caractère endothermique.Once hardened the resins form matrices which have good physical properties and mechanical and excellent endothermic character.

    Elles peuvent être utilisées comme protection contre des agressions thermiques en tant que structure autoportante ou revêtement.They can be used as protection against thermal stress as a structure freestanding or cladding.

    Une ou plusieurs charges très diverses, organiques, minérales et/ou métalliques peuvent être incorporées dans les résines avant durcissement. Les charges sont généralement sous forme granulaire ou fibreuse. Avantageusement ce sont des substances minérales.One or more very diverse, organic fillers, mineral and / or metallic can be incorporated in resins before hardening. The charges are usually in granular or fibrous form. Advantageously, these are mineral substances.

    La proportion de charges est au maximum de 50% en volume par rapport au volume total de la résine et des charges.The proportion of charges is at most 50% in volume relative to the total volume of the resin and charges.

    Comme exemple de charges, on peut citer les sulfates, les oxydes et les hydroxydes alcalino-terreux, en particulier ceux de calcium, de magnésium, l'alumine, les hydrates d'alumine, l'oxyde de zinc, le borax et les aluminosilicates.As an example of charges, mention may be made of sulfates, alkaline earth oxides and hydroxides, especially those of calcium, magnesium, alumina, alumina hydrates, zinc oxide, borax and aluminosilicates.

    D'autres constituants habituels de résines pourront également être ajoutés tels que des pigments, des adjuvants.Other usual constituents of resins may also be added such as pigments, adjuvants.

    Un autre objet de la présente invention concerne le procédé de préparation de ces nouvelles résines. Another object of the present invention relates to the process for the preparation of these new resins.

    Ce procédé consiste à effectuer un mélange homogène des deux précurseurs suivants préparés séparément :

  • I) un précurseur qui est une poudre constituée d'un aluminosilicate obtenu par amorphisation d'une argile 1 : 1 dans laquelle le rapport atomique Si / Al est égal à 1 ;
  • II) Un précurseur liquide qui est une solution aqueuse alcaline contenant, à l'état dissous, au moins un élément alcalin choisi parmi le sodium, le potassium et le lithium, du bore et éventuellement du silicium, le bore pouvant être présent en quantité supérieure à sa saturation ;
    • les quantités des différents constituants étant déterminées pour que leurs rapports molaires dans le mélange exprimés en terme d'oxyde, aient les valeurs suivantes :
  • 2 ≤ Si02/Al203 ≤ 4
  • 1,3 ≤ X20/Al203 ≤ 3,8
  • 10 ≤ H20/Al203 ≤ 28
  • 0,5< B203/Al203 ≤ 2,0
    •  X20 représentant un ou plusieurs oxydes alcalins choisis parmi Na20, K20 et Li20.This process consists in carrying out a homogeneous mixture of the following two precursors prepared separately:
  • I) a precursor which is a powder consisting of an aluminosilicate obtained by amorphization of a clay 1: 1 in which the atomic ratio Si / Al is equal to 1;
  • II) A liquid precursor which is an aqueous alkaline solution containing, in the dissolved state, at least one alkaline element chosen from sodium, potassium and lithium, boron and optionally silicon, the boron being able to be present in higher quantity at its saturation;
    • the quantities of the various constituents being determined so that their molar ratios in the mixture, expressed in terms of oxide, have the following values:
  • 2 ≤ Si0 2 / Al 2 0 3 ≤ 4
  • 1.3 ≤ X 2 0 / Al 2 0 3 ≤ 3.8
  • 10 ≤ H 2 0 / Al 2 0 3 ≤ 28
  • 0.5 <B 2 0 3 / Al 2 0 3 ≤ 2.0
    • X 2 0 representing one or more alkaline oxides chosen from Na 2 0, K 2 0 and Li 2 0.

    On obtient ainsi une résine suffisamment fluide qui peut être durcie immédiatement.A sufficiently fluid resin is thus obtained which can be cured immediately.

    Avantageusement X20 représente Na20, K20 ou un mélange de Na20 et de K20, de Li20 et de Na20, de Li20 et de K20 ou de Li20, de Na20 et de K20.Advantageously X 2 0 represents Na 2 0, K 2 0 or a mixture of Na 2 0 and K 2 0, Li 2 0 and Na 2 0, Li 2 0 and K 2 0 or Li 2 0, Na 2 0 and K 2 0.

    Selon un procédé préféré, les rapports molaires des oxydes dans le mélange ont les valeurs suivantes :

  • 3,0 ≤ Si02/Al203 ≤ 3,8
  • 1,5 ≤ X20/Al203 ≤ 3,6
  • 13,0 ≤ H20/Al203 ≤ 19,5
  • 0,5< B203/Al203 ≤ 1,8
    • X20 représentant l'oxyde de potassium ou les valeurs suivantes :
  • 2,0 ≤ Si02/Al203 ≤ 3,9
  • 1,4 ≤ X20/Al203 ≤ 3,0
  • 10 ≤ H20/Al203 ≤ 28,0
  • 0,5< B203/Al203 ≤ 1,3
    •  X20 représentant l'oxyde de sodium ou un mélange d'oxyde de sodium et de potassium.According to a preferred method, the molar ratios of the oxides in the mixture have the following values:
  • 3.0 ≤ Si0 2 / Al 2 0 3 ≤ 3.8
  • 1.5 ≤ X 2 0 / Al 2 0 3 ≤ 3.6
  • 13.0 ≤ H 2 0 / Al 2 0 3 ≤ 19.5
  • 0.5 <B 2 0 3 / Al 2 0 3 ≤ 1.8
    • X 2 0 representing potassium oxide or the following values:
  • 2.0 ≤ Si0 2 / Al 2 0 3 ≤ 3.9
  • 1.4 ≤ X 2 0 / Al 2 0 3 ≤ 3.0
  • 10 ≤ H 2 0 / Al 2 0 3 ≤ 28.0
  • 0.5 <B 2 0 3 / Al 2 0 3 ≤ 1.3
    • X 2 0 representing sodium oxide or a mixture of sodium and potassium oxide.

    Les argiles 1 : 1 qui constituent la matière première du précurseur en poudre se trouvent dans le commerce. Il est préférable qu'elles soient finement broyées, et, pour obtenir une meilleure réactivité, on utilise de préférence celles dont les grains ont une dimension inférieure à 5 µm. En général l'argile utilisée est du kaolin et de préférence dont la teneur en kaolinite est supérieure à 70%.The 1: 1 clays that make up the material first of the powder precursor are found in the trade. It is better that they are finely ground, and to get better reactivity, we preferably use those whose grains have a dimension less than 5 µm. In general clay used is kaolin and preferably whose content in kaolinite is greater than 70%.

    Les argiles doivent être amorphisées afin de les rendre réactives avec le précurseur liquide. L'amorphisation peut être obtenue selon des procédés connus. Un procédé qui convient bien dans le cadre de la présente invention est le traitement thermique des argiles de préférence à une température comprise entre 600° C et 1100° C. La durée du traitement est fonction de la température. A 700° C cette durée est de l'ordre de quelques heures. A 1000° C quelques secondes peuvent suffire pour obtenir cette amorphisation. Une autre façon de réaliser l'amorphisation des argiles consiste à les disperser dans des acides forts et concentrés tels que l'acide chlorhydrique, l'acide sulfurique ou l'acide nitrique. On peut effectuer successivement plusieurs traitements d'amorphisation différents. Lorsqu'on effectue les deux traitements précédents on préfère généralement réaliser le traitement à l'acide avant le traitement thermique. L'amorphisation des argiles peut être constatée par l'examen de leurs spectres de diffraction aux rayons X dans lesquels ne doit apparaítre ni le spectre de cristallisation de la kaolinite, ni les spectres des phases cristallines qui naissent à une température supérieure à 1100° C.The clays must be amorphized in order to make reactive with the liquid precursor. Amorphization can be achieved by methods known. A process that is well suited in the context of present invention is the heat treatment of clays preferably at a temperature between 600 ° C and 1100 ° C. The duration of treatment is a function of the temperature. At 700 ° C this duration is around of a few hours. At 1000 ° C a few seconds can suffice to obtain this amorphization. Another way to achieve the amorphization of clays is to disperse them in strong and concentrated acids such than hydrochloric acid, sulfuric acid or acid nitric. We can perform successively several different amorphization treatments. When we perform the two previous treatments we prefer generally carry out the acid treatment before heat treatment. Amorphization of clays can be ascertained by examining their spectra of X-ray diffraction in which should not appear neither the crystallization spectrum of the kaolinite, nor the spectra of the crystalline phases which are born at a temperature above 1100 ° C.

    Le précurseur liquide est une solution aqueuse qui doit contenir, à l'état dissous, au moins un élément alcalin choisi parmi le sodium, le potassium et le lithium, du bore, celui-ci pouvant être en état de sursaturation, et éventuellement du silicium.The liquid precursor is an aqueous solution which must contain, in the dissolved state, at least one element alkaline chosen from sodium, potassium and lithium, boron, which may be in a state of supersaturation, and possibly silicon.

    Afin d'obtenir un précurseur liquide stable il est nécessaire d'une part que tous les constituants soient bien dissous pour former une solution. Cet état dissous est également nécessaire pour que ces constituants puissent former avec les autres constituants du précurseur en poudre le squelette de la résine. D'autre part le précurseur liquide ne doit pas être trop visqueux afin de pouvoir être mélangé avec le précurseur en poudre et afin d'obtenir une résine suffisamment fluide qui puisse être moulée ou façonnée et contenir éventuellement des charges ou qui puisse servir à l'imprégnation. De préférence la viscosité du précurseur liquide est inférieure ou égale à 30 poises.In order to obtain a stable liquid precursor it is firstly that all the constituents are well dissolved to form a solution. This dissolved state is also necessary for these constituents can form with the other constituents of the powder precursor the skeleton of the resin. Else apart the liquid precursor should not be too viscous so that it can be mixed with the precursor in powder and in order to obtain a sufficient resin fluid that can be molded or shaped and contain possibly charges or that can be used to impregnation. Preferably the viscosity of the precursor liquid is less than or equal to 30 poises.

    Les éléments alcalins sont généralement introduits dans le milieu aqueux, au moyen des hydroxydes alcalins, Na0H, K0H et/ou Li0H.Alkaline elements are usually introduced in the aqueous medium, by means of alkali hydroxides, Na0H, K0H and / or Li0H.

    Le bore est introduit au moyen d'une de ses formes et/ou d'au moins un de ses composés capable de se dissoudre dans un milieu aqueux et alcalin tels que par exemple un oxyde, sel, acide ou hydroxyde. Avantageusement on utilise l'acide orthoborique. Lorsqu'on souhaite obtenir une résine avec une grande proportion de bore, le précurseur liquide doit contenir une très grande quantité de cet élément et il est possible que pour un rapport B203/Al203 ≥ 1,1, la solution contienne un précipité à base de bore.Boron is introduced by means of one of its forms and / or at least one of its compounds capable of dissolving in an aqueous and alkaline medium such as for example an oxide, salt, acid or hydroxide. Advantageously, orthoboric acid is used. When it is desired to obtain a resin with a large proportion of boron, the liquid precursor must contain a very large quantity of this element and it is possible that for a ratio B 2 0 3 / Al 2 0 3 ≥ 1.1, the solution contains a boron-based precipitate.

    Lorsqu'on veut introduire du silicium dans le précurseur liquide, celui-ci est ajouté sous la forme d'un silicate alcalin, de sodium et/ou de potassium dans le milieu aqueux.When we want to introduce silicon into the liquid precursor, this is added in the form of an alkali, sodium and / or potassium silicate in the aqueous medium.

    Pour obtenir le précurseur liquide on préfère généralement introduire dans l'eau d'abord le(s) hydroxyde(s) alcalin(s) puis éventuellement le(s) silicate(s) et enfin le(s) composé(s) du bore. On peut chauffer le mélange afin de favoriser une bonne homogénéité.To obtain the liquid precursor we prefer generally introduce into the water first the alkali hydroxide (s) then optionally the (s) silicate (s) and finally the boron compound (s). We can heat the mixture to promote good homogeneity.

    Le mélange du précurseur liquide et du précurseur en poudre s'effectue à la température ambiante, par exemple au moyen d'un mélangeur à hélice. On obtient rapidement une résine homogène coulable ou façonnable qui pourra servir à fabriquer des objets par les techniques habituelles notamment par moulage. Cette résine peut ensuite être durcie sans qu'un temps de repos soit nécessaire. Le durcissement résulte de la réaction qui se produit et qui peut s'apparenter à une réaction d'hydrolyse-polycondensation. On peut faire durcir la résine telle quelle ou bien après l'avoir mélangée avec des charges minérales, métalliques et/ou organiques telles que précédemment décrites ou après avoir imprégné des fibres ou des matériaux comprenant des fibres tels que des mats et des tissus.The mixture of the liquid precursor and the precursor powder is carried out at room temperature, by example using a propeller mixer. We obtain quickly a homogeneous resin which can be poured or shaped which can be used to make objects by usual techniques including molding. This resin can then be cured without time rest is required. The hardening results from the reaction that occurs and which can be akin to a hydrolysis-polycondensation reaction. We can do harden the resin as it is or after having mixed with mineral, metallic and / or organic as previously described or after having impregnated fibers or materials comprising fibers such as mats and fabrics.

    Le durcissement peut être effectué à une température comprise entre 0° et 150° C. Jusqu'à la température ambiante, voisine de 20° C, il est lent. On préfère chauffer la résine à une température comprise entre 40° et 120° C. Le temps de durcissement varie en fonction de la formulation de la résine, de la température et du mode de chauffage utilisé. Au moyen d'un chauffage classique par apport thermique extérieur, certaines formulations durcissent en moins d'une heure à 80° C. Au moyen d'un chauffage par micro-ondes quelques secondes peuvent suffire.Curing can be done at a temperature between 0 ° and 150 ° C. Until room temperature, around 20 ° C, it is slow. We prefer to heat the resin to a temperature between 40 ° and 120 ° C. The hardening time varies in depending on the formulation of the resin, the temperature and the heating mode used. Thanks to conventional heating by external heat input, some formulations cure in less than an hour at 80 ° C. By means of microwave heating a few seconds may be enough.

    Il est nécessaire que le durcissement soit réalisé en présence de la totalité de l'eau présente dans la résine. On doit opérer par conséquent en milieu hermétique ou saturé en eau.Curing is necessary in the presence of all the water present in the resin. We must therefore operate in the middle airtight or saturated with water.

    Lorsque la réaction de durcissement est très avancée, on peut la laisser se terminer dans les conditions de température et d'hygrométrie ambiantes, de préférence après avoir au préalable refroidi le matériau jusqu'à une température voisine de la température ambiante. Un séchage, par exemple en étuve, peut éventuellement être effectué ensuite.When the curing reaction is very advanced, we can let it end in ambient temperature and humidity conditions, preferably after having previously cooled the material up to a temperature close to the temperature ambient. Drying, for example in an oven, can possibly be performed next.

    Lorsqu'on fabrique des objets moulés avec les résines selon l'invention, il ne se produit pratiquement pas de retrait. Les objets ont une bonne dureté de surface. Ils ne présentent ni fissuration ni déformation et possèdent de bonnes propriétés mécaniques.When making molded objects with resins according to the invention it practically does not occur no withdrawal. Objects have a good hardness of area. They show no cracking or deformation and have good mechanical properties.

    En raison de leur forte endothermicité, les résines selon la présente invention sont particulièrement utiles comme matériaux de protection thermique et en particulier comme barrière anti-feu. Elles peuvent être moulées sous différentes formes et par exemple sous forme de panneaux. Les tests effectués avec des panneaux d'épaisseur comprise entre 10 et 30 mm d'épaisseur montrent que ces matériaux sont tout à fait utilisables contre des agressions thermiques telles qu'en particulier une montée progressive en température jusqu'à 1200° environ ou un flash thermique d'une dizaine de minutes à 850° C.Due to their high endothermicity, resins according to the present invention are particularly useful as thermal protection materials and especially as a fire barrier. They can be molded in different forms and for example under form of panels. Tests performed with panels between 10 and 30 mm thick show that these materials are quite usable against thermal attacks such as particularly a gradual rise in temperature up to around 1200 ° or a thermal flash of ten minutes at 850 ° C.

    On peut encore améliorer le caractère d'isolation thermique des objets moulés à base des résines selon l'invention en liant sur une ou plusieurs faces de l'objet un élément réflecteur de chaleur qui peut être constitué par exemple par une couche très fine de mica ou de paillettes d'un métal amorphe appelé "verre métallique" placée sur la ou les face(s) de l'objet et maintenue par un mat de verre imprégné d'une résine minérale non chargée telle que décrite précédemment qui par durcissement effectuera la liaison. L'élément réflecteur est placé sur une ou plusieurs faces à l'intérieur du moule qui recevra la résine et se trouvera lié à(aux) face(s) de l'objet après durcissement de l'ensemble.We can still improve the insulation character thermal of molded objects based on resins according to the invention by binding on one or more faces of the object a heat reflective element which can be consisting for example of a very thin layer of mica or flakes of an amorphous metal called "glass metallic "placed on the face (s) of the object and held by a glass mat impregnated with a resin uncharged mineral as described above which by hardening will bond. The element reflector is placed on one or more faces to inside the mold which will receive the resin and will find related to the face (s) of the object after hardening of the whole.

    Les exemples qui suivent illustrent l'invention sans toutefois la limiter.The following examples illustrate the invention without however limiting it.

    Exemples 1 à 8Examples 1 to 8

    On prépare différentes résines selon l'invention à partir des composés et de la manière indiqués ci-dessous :Different resins according to the invention are prepared at from the compounds and as shown below :

    Précurseur en poudre :Powder precursor:

    On utilise du kaolin amorphisé par traitement thermique de provenances diverses :

  • A1 : Kaolin "B 24" commercialisé par la société Blancs Minéraux de Paris, traité thermiquement à 800° C pendant 4 heures.
  • A2 : Kaolin "GRADE B" commercialisé par la société English China Clay, traité thermiquement à 800° C pendant 4 heures.
  • A3 : Kaolin "SUPREME" commercialisé par la société English China Clay, traité thermiquement à 800° C pendant 4 heures.
  • A4 : Kaolin "Polestar 501" commercialisé par la société English China Clay.
    • We use kaolin amorphized by heat treatment from various sources:
  • A 1 : Kaolin "B 24" sold by the company Blancs Minéraux de Paris, heat treated at 800 ° C for 4 hours.
  • A 2 : Kaolin "GRADE B" sold by the company English China Clay, heat treated at 800 ° C for 4 hours.
  • A 3 : Kaolin "SUPREME" sold by the company English China Clay, heat treated at 800 ° C for 4 hours.
  • A 4 : Kaolin "Polestar 501" sold by the company English China Clay.

    • Précurseur liquide :Liquid precursor:

    On l'obtient en introduisant de façon progressive dans de l'eau distillée différentes quantités des composés suivants :

  • la soude en pastilles (mN)
  • la potasse en pastilles (mK)
  • le silicate de potassium de formule K20, 3Si02, 3H20 (nK)
  • le silicate de sodium de formule Na20, 3Si02, 3H20 (nN)
  • l'acide orthoborique en poudre, H3BO3 (aob)
    • It is obtained by gradually introducing into distilled water different amounts of the following compounds:
  • soda in pellets (m N )
  • potash in pellets (m K )
  • potassium silicate of formula K 2 0, 3Si0 2 , 3H 2 0 (n K )
  • sodium silicate of formula Na 2 0, 3Si0 2 , 3H 2 0 (n N )
  • orthoboric acid powder, H 3 BO 3 (aob)

    • Les termes entre parenthèses sont utilisés dans les tableaux suivants pour représenter les quantités en grammes des composés. La lettre h sera utilisée pour désigner la quantité d'eau en grammes.The terms in parentheses are used in following tables to represent the quantities in grams of the compounds. The letter h will be used for designate the amount of water in grams.

    Généralement on introduit en premier le ou le(s) hydroxyde(s) ensuite le ou le(s) silicate(s) puis l'acide orthoborique.Generally we introduce first the hydroxide (s) then the silicate (s) then orthoboric acid.

    On agite et on chauffe éventuellement le mélange afin d'obtenir une bonne homogénéité.The mixture is stirred and optionally heated in order to obtain good homogeneity.

    Pour obtenir la résine, on effectue le mélange des deux précurseurs à la température ambiante en incorporant progressivement la poudre dans la solution liquide dans des proportions indiquées par le rapport suivant : LA = masse du précurseur liquidemasse du précurseur poudre To obtain the resin, the two precursors are mixed at room temperature by gradually incorporating the powder into the liquid solution in the proportions indicated by the following report: L AT = mass of liquid precursor mass of powder precursor

    On agite pendant 15 minutes environ puis lorsqu'on veut obtenir une résine chargée on incorpore 10% en volume par rapport au volume total de la résine et des charges, d'une ou de plusieurs des charges suivantes. Lorsqu'il y a plusieurs charges, elles sont ajoutées en proportions égales. Les abréviations utilisées sont indiquées entre parenthèses.

  • Alumine : "SPHER 200-500" vendu par la société DURMAX (Sp25)
  • BORAX (Bx)
    Aluminosilicates :
    PORAVER 1-2 (P12)
    PORAVER 2-4 (P24)
    PORAVER 0,25-0,5 (P02505)
  • vendus par la société PORAVER
  • Alumine trihydratée (ATH)
  • Oxyde de zinc en poudre (Z)
  • Oxyde de magnésium, densité 0,2 (M)
  • Hydroxyde de calcium (C)
  • Sulfate de calcium (SC)
  • Sulfate de magnésium (SM).
    • The mixture is stirred for approximately 15 minutes then, when a charged resin is to be obtained, 10% by volume relative to the total volume of the resin and of the fillers, of one or more of the following fillers are incorporated. When there are several charges, they are added in equal proportions. The abbreviations used are indicated in parentheses.
  • Alumina: "SPHER 200-500" sold by the company DURMAX (Sp25)
  • BORAX (Bx)
    Aluminosilicates:
    PORAVER 1-2 (P12)
    PORAVER 2-4 (P24)
    PORAVER 0.25-0.5 (P02505)
  • sold by PORAVER
  • Alumina trihydrate (ATH)
  • Zinc oxide powder (Z)
  • Magnesium oxide, density 0.2 (M)
  • Calcium hydroxide (C)
  • Calcium sulfate (SC)
  • Magnesium sulfate (SM).

    • On mélange vigoureusement la résine et les charges pendant 10 minutes environ.The resin and the fillers are vigorously mixed for about 10 minutes.

    La résine seule ou contenant les charges est ensuite coulée dans une boíte en polyéthylène qui est fermée hermétiquement. On ne laisse pas reposer l'ensemble, le durcissement est effectué immédiatement en plaçant la boíte dans une étuve à 60° C. A cette température la prise en masse de la résine chargée ou non s'effectue généralement en moins de 15 heures. Certaines compositions durcissent en moins de 5 heures.The resin alone or containing the fillers is then poured into a polyethylene box which is hermetically closed. We don't let it sit the whole, hardening is carried out immediately placing the box in an oven at 60 ° C. At this temperature the solidification of the loaded resin or no generally takes less than 15 hours. Some compositions cure in less than 5 hours.

    On démoule la pièce obtenue une heure après la sortie de l'étuve et on note l'aspect de cette pièce selon les critères suivants :

  • a : pièce monolithique, résistance à une pression manuelle bonne - surface dure non rayée par l'ongle - pas de retrait ni de déformation
  • b : pièce monolithique, résistance à une pression manuelle et surface dure obtenues après avoir laissé le durcissement se terminer à la température ambiante - pas de fissuration ni de déformation.
    • The part obtained is removed from the mold one hour after leaving the oven and the appearance of this part is noted according to the following criteria:
  • a: monolithic part, resistance to good manual pressure - hard surface not scratched by the nail - no shrinkage or deformation
  • b: monolithic part, resistance to manual pressure and hard surface obtained after allowing hardening to finish at room temperature - no cracking or deformation.

    • Les résultats des essais sont rassemblés dans les tableaux I et II ci-après.The results of the tests are collected in the Tables I and II below.

    Les rapports molaires d'oxydes sont désignés par les abréviations suivantes :

    S :
    Si02/Al203
    K :
    K20/Al2O3
    N :
    Na20/Al203
    NK :
    Na20 + K20/Al203
    H :
    H20/Al203
    B :
    B203/Al203
    The molar ratios of oxides are designated by the following abbreviations:
    S:
    Si0 2 / Al 2 0 3
    K:
    K 2 0 / Al 2 O 3
    NOT :
    Na 2 0 / Al 2 0 3
    NK:
    Na 2 0 + K 2 0 / Al 2 0 3
    H:
    H 2 0 / Al 2 0 3
    B:
    B 2 0 3 / Al 2 0 3

    Dans la ligne composition de prise en masse lorsque la résine est durcie seule elle est notée par R. Lorsqu'elle contient des charges celles-ci sont indiquées par leurs abréviations. Lorsque plusieurs types de charges sont utilisés, ils sont indiqués entre parenthèses.In the line composition of solidification when the resin is hardened alone it is noted by R. When it contains charges these are indicated by their abbreviations. When several types of charges are used, they are indicated between parentheses.

    Exemples 9 et 10Examples 9 and 10

    Afin de montrer la propriété de protection thermique des résines selon l'invention on effectue le test suivant :In order to show the protective property thermal resins according to the invention the following test:

    On fabrique des plaques de dimensions 300 x 300 mm2 et d'épaisseur 30mm que l'on soumet à une agression thermique selon la norme ISO 834 sur une face et l'on détermine le temps nécessaire pour que l'autre face, arrière, atteigne les températures de 100° et 170°.Plates with dimensions 300 x 300 mm 2 and thickness 30 mm are produced which are subjected to thermal aggression according to ISO standard 834 on one side and the time required for the other side, rear, to be determined, reaches temperatures of 100 ° and 170 °.

    Les plaques sont obtenues en introduisant dans un moule, les compositions ci-après de résines, préparées comme indiqué dans les exemples précédents.The plates are obtained by introducing into a mold, the following compositions of resins, prepared as shown in the previous examples.

    Sur les faces supérieure et inférieure du moule on place préalablement un mat de verre classique à 300g/m2 imprégné d'une des résines minérales de l'invention présentant un durcissement rapide et sur ce mat une couche d'environ 0,2 millimètre d'épaisseur constituée par des paillettes de verre métallique de longueur 30mm, FIBRAFLEX vendu par la société SEVA. Le moule est placé entre les plateaux d'une presse dont la température est de 100° C. On exerce une pression de 2 à 3 bars (0,2 à 0,3MPa) afin de faire fluer la matière et de remplir le moule qui est complètement fermé.On the upper and lower faces of the mold, a conventional glass mat at 300 g / m 2 impregnated with one of the mineral resins of the invention having a rapid hardening is placed beforehand and on this mat a layer of approximately 0.2 mm d thickness consisting of metallic glass flakes with a length of 30mm, FIBRAFLEX sold by the company SEVA. The mold is placed between the plates of a press whose temperature is 100 ° C. A pressure of 2 to 3 bars (0.2 to 0.3 MPa) is exerted in order to make the material flow and to fill the mold which is completely closed.

    Les résultats sont indiqués dans le tableau III ci-après.The results are shown in Table III below.

    Exemples 11 et 12Examples 11 and 12

    Afin de montrer la propriété de protection thermique des résines selon l'invention lors d'une agression thermique brutale de 850° C pendant 10 minutes on effectue le test suivant :In order to show the protective property thermal resins according to the invention during a brutal thermal attack of 850 ° C for 10 minutes the following test is carried out:

    On remplace la porte d'un four électrique porté à 850° C par une plaque d'épaisseur comprise entre 10,5 et 11 mm et on laisse cette plaque en place pendant 10 minutes. On écarte ensuite la plaque du four et on relève la température maximale atteinte par la face non exposée.We replace the door of an electric oven brought to 850 ° C by a plate thickness between 10.5 and 11 mm and leave this plate in place for 10 minutes. Then remove the baking sheet and notes the maximum temperature reached by the side not exposed.

    Les plaques sont réalisées comme précédemment par introduction dans un moule des compositions résineuses préparées comme indiqué dans les exemples 1 à 8. Seule la face placée du côté de l'agression thermique et les côtés comportent éventuellement un réflecteur constitué par un mat de verre à 50g/m2 imprégné d'une résine minérale selon l'invention à durcissement rapide et par une couche d'environ 0,2 mm d'épaisseur de paillettes FIBRAFLEX de longueur 15mm.The plates are produced as before by introduction into a mold of the resinous compositions prepared as indicated in examples 1 to 8. Only the face placed on the side of the thermal attack and the sides optionally include a reflector constituted by a glass mat of 50 g / m 2 impregnated with a quick-hardening mineral resin according to the invention and with a layer of approximately 0.2 mm thick FIBRAFLEX flakes 15 mm long.

    Les résultats sont indiqués ci-dessous : Exemples 11 12 Précurseur poudre A4 A3 Précurseur liquide L2 L7 L/A 2,93 2,93 Charges (% massique par rapport à la masse totale résine plus charges) SC (12) et P12 (12,7) M (5) et P02505 (17) Réflecteur Oui Non Température maximale de la face non exposée 235° C 216° C The results are shown below: Examples 11 12 Powder precursor A4 A3 Liquid precursor L2 L7 THE 2.93 2.93 Fillers (% by mass relative to the total resin mass plus fillers) SC (12) and P12 (12.7) M (5) and P02505 (17) Reflector Yes No Maximum temperature of the unexposed face 235 ° C 216 ° C

    Exemples 13 et 14Examples 13 and 14

    On prépare des résines contenant comme éléments alcalins du potassium et du lithium, selon le mode opératoire décrit dans les exemples 1 à 8.Resins are prepared containing as elements potassium and lithium alkalies, depending on mode procedure described in examples 1 to 8.

    Le lithium est introduit sous forme de lithine (Li0H) en poudre.Lithium is introduced in the form of lithine (Li0H) powder.

    La préparation du précurseur liquide s'opère par dissolution complète des ingrédients dans l'ordre suivant :

    • 1 Dissolution de la lithine dans l'eau,
    • 2 Ajout de la potasse,
    • 3 Ajout du silicate de potassium en poudre ou sous forme liquide,
    • 4 Ajout de l'acide orthoborique.
    The liquid precursor is prepared by completely dissolving the ingredients in the following order:
    • 1 Dissolution of lithine in water,
    • 2 Adding potash,
    • 3 Addition of potassium silicate in powder or liquid form,
    • 4 Addition of orthoboric acid.

    A chaque opération, il faut attendre que les différents composés formés se dissolvent. Ces opérations se déroulent à froid, le chauffage entraínant la formation d'espèces insolubles. At each operation, wait until the different compounds formed dissolve. These operations take place cold, the heating causing the formation of insoluble species.

    Les caractéristiques des résines sont les suivantes : EXEMPLES 13 14 Référence de la poudre A4 A4 Précurseur liquide h 108,3 108,3 nK 35 35 mK 46,7 46,7 mL 5,6 7,2 aob 35 35 L/A 2,5 2,5 S ; KT ; H 3,0;1,6;20,2 3,0;1,7;20,2 B 0,7 0,7 Composition de prise en masse R R Aspect des monolithes après démoulage a a Temps de prise à 60°C 24 heures 24 heures - mL représente la quantité en grammes de lithine contenue dans le précurseur liquide
    - KT représente le rapport molaire Li20 + K20/Al203

    Figure 00160001
    Figure 00170001
    EXEMPLE 9 10 PRECURSEUR LIQUIDE L2 L7 PRECURSEUR POUDRE A2 A2 L/A 2,93 2,94 CHARGES (% EN MASSE PAR RAPPORT A LA MASSE DE LA RESINES PLUS LES CHARGES) Bx (8%) P24 (50%) P24 (42%) DENSITE AVANT ESSAI 0,76 0,68 MASSE SURFACIQUE AVANT ESSAI 23 kg/m2 20,5 kg/m2 DEGRE COUPE-FEU SELON ISO 834 (heures, minutes) 1H03 1H00 TEMPS POUR ATTEINDRE 100° 53 min 53 min The characteristics of the resins are as follows: EXAMPLES 13 14 Powder reference A4 A4 Liquid precursor h 108.3 108.3 n K 35 35 m K 46.7 46.7 m L 5.6 7.2 aob 35 35 THE 2.5 2.5 S; KT; H 3.0; 1.6; 20.2 3.0; 1.7; 20.2 B 0.7 0.7 Bulking composition R R Appearance of the monoliths after demolding at at Setting time at 60 ° C 24 hours 24 hours - m L represents the quantity in grams of lithine contained in the liquid precursor
    - KT represents the molar ratio Li 2 0 + K 2 0 / Al 2 0 3
    Figure 00160001
    Figure 00170001
    EXAMPLE 9 10 LIQUID PRECURSOR L2 L7 POWDER PRECURSOR A2 A2 THE 2.93 2.94 LOADS (% IN MASS IN RELATION TO THE MASS OF THE RESINS PLUS THE LOADS) Bx (8%) P24 (50%) P24 (42%) DENSITY BEFORE TEST 0.76 0.68 SURFACE MASS BEFORE TEST 23 kg / m 2 20.5 kg / m 2 DEGREE FIRE-RESISTANT ACCORDING TO ISO 834 (hours, minutes) 1H03 1H00 TIME TO REACH 100 ° 53 mins 53 mins

    Claims (16)

    1. Hardenable inorganic resins, characterized in that they are based on alkaline boroaluminosilicates and in that they contain, before hardening, inorganic elements in the reactive state, boron being also capable of being in a supersaturated state, in the following proportions expressed by the molar ratio of their oxides :
      2 ≤ SiO2/Al2O3 ≤ 4
      1.3 ≤ X2O/Al2O3 ≤ 3.8
      10 ≤ H2O/Al2O3 ≤ 28
      0.5 < B2O3/Al2O3 ≤ 2.0
      X2O representing one or more alkali metal oxides selected from Na2O, K2O and Li2O
    2. Inorganic resins according to claim 1, characterized in that X2O represents Na2O, K2O or a mixture of Na2O and K2O or of Li2O and Na2O or of Li2O and K2O or of Li2O, Na2O and K2O.
    3. Inorganic resins according to claim 1, characterized in that the molar ratios of the oxides have the following values :
      3.0 ≤ SiO2/Al2O3 ≤ 3.8
      1.5 ≤ X2O/Al2O3 ≤ 3.6
      13.0 ≤ H2O/Al2O3 ≤ 19.5
      0.5 < B2O3/Al2O3 ≤ 1.8
      X2O representing K2O or
      2.0 ≤ SiO2/Al2O3 ≤ 3.9
      1.4 ≤ X2O/Al2O3 ≤ 3.0
      10.0 ≤ H2O/Al2O3 ≤ 28.0
      0.5 < B2O3/Al2O3 ≤ 1.3
      X2O representing Na2O or a mixture of Na2O and K2O.
    4. Inorganic resins according to claim 1, characterized in that they contain one or more fillers selected from inorganic, metallic and/or organic fillers.
    5. Inorganic resins according to claim 1 or 4, characterized in that they contain one or more inorganic fillers, preferably selected from the sulphates, oxides and hydroxides of alkaline earths, alumina, alumina hydrates, zinc oxide, borax and aluminosilicates.
    6. Inorganic resins according to claim 1 or 4, characterized in that they are in the hardened form.
    7. Process for preparing inorganic resins according to claim 1, characterized in that a homogeneous mixture is prepared of the following two precursors, prepared separately :
      I) a precursor which is a powder consisting of an aluminosilicate obtained by amorphization of a 1 : 1 clay in which the atomic ratio Si/Al is equal to 1 ;
      II) a liquid precursor which is an alkaline aqueous solution containing, in the dissolved state, at least one alkali metal element selected from sodium, potassium and lithium, boron and possibly silicon, it being possible for boron to be present in a quantity greater than its saturation quantity ;
      the quantities of the various constituents being determined so that their molar ratios in the mixture, expressed in terms of the oxides, have the following values :
      2.0 ≤ SiO2/Al2O3 ≤ 4
      1.3 ≤ X2O/Al2O3 ≤ 3.8
      10 ≤ H2O/Al2O3 ≤ 28
      0.5 < B2O3/Al2O3 ≤ 2.0
      X2O representing one or more alkali metal oxides selected from Na2O, K2O and Li2O.
    8. Process according to claim 7, characterized in that X2O represents Na2O, K2O or a mixture of Na2O and K2O or of Li2O and Na2O or of Li2O and K2O or of Li2O, Na2O and K2O.
    9. Process according to claim 7 characterized in that the molar ratios of the oxides have the following values :
      3.0 ≤ SiO2/Al2O3 ≤ 3.8
      1.5 ≤ X2O/Al2O3 ≤ 3.6
      13.0 ≤ H2O/Al2O3 ≤ 19.5
      0.5 < B2O3/Al2O3 ≤ 1.8
      X2O representing K2O or
      2.0 ≤ SiO2/Al2O3 ≤ 3.9
      1.4 ≤ X2O/Al2O3 ≤ 3.0
      10.0 ≤ H2O/Al2O3 ≤ 28.0
      0.5 < B2O3/Al2O3 ≤ 1.3
      X2O representing Na2O or a mixture of Na2O and K2O.
    10. Process according to claim 7 characterized in that amorphization of clay is obtained by treatment with concentrated strong acids and/or by heat treatment.
    11. Process according to claim 7, characterized in that the resins are hardened in the presence of all the water that they contain, at a temperature of between 0°C and 150°C.
    12. Process according to claim 11, characterized in that before hardening, the resin is mixed with one or more inorganic, metallic and/or organic fillers or is used to impregnate fibres or fibre-containing materials.
    13. Process according to claim 11, characterized in that before hardening, the resin is mixed with one or more inorganic fillers, preferably selected from the sulphates, oxides and hydroxides of alkaline earths, alumina, alumina hydrates, zinc oxide, borax and aluminosilicates.
    14. Object characterized in that it contains a resin according to claim 1, 4 or 6.
    15. Materials for heat protection, characterized in that they are obtained by moulding and hardening a resin according to claim 1 or 4.
    16. Materials according to claim 15, characterized in that there is attached to one or more faces of the material a heat reflecting component consisting of a very fine layer of mica or of metallic glass flakes placed on the face or faces of the material and held by a glass mat impregnated with an unfilled resin such as is described in claim 1 and hardened to achieve the bond.
    EP94401440A 1993-07-06 1994-06-27 Inorganic resins, process for their preparation and thermal protection articles Expired - Lifetime EP0633231B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    FR9308238A FR2707286B1 (en) 1993-07-06 1993-07-06 Mineral resins, their preparation process and materials for thermal protection.
    FR9308238 1993-07-06

    Publications (2)

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    EP0633231A1 EP0633231A1 (en) 1995-01-11
    EP0633231B1 true EP0633231B1 (en) 1998-06-03

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    EP (1) EP0633231B1 (en)
    DE (1) DE69410702D1 (en)
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    Publication number Priority date Publication date Assignee Title
    FR2778239B1 (en) 1998-05-04 2000-05-26 Poudres & Explosifs Ste Nale METHOD AND PLANT FOR DESTRUCTION OF AMMUNITION CONTAINING TOXIC AGENTS USING HOT GASES
    US20040050384A1 (en) * 2002-09-17 2004-03-18 Lawrence Stein Fire-resistant containers made using inorganic polymer material
    US7745363B2 (en) * 2005-05-09 2010-06-29 Corning Incorporated Geopolymer composites and structures formed therefrom

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    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3250725A (en) * 1961-07-11 1966-05-10 Victor C Vescovi Method for producing boro-silica gels
    DE2210837A1 (en) * 1972-03-07 1973-09-20 Bayer Ag PROCESS FOR THE MANUFACTURING OF SHAPED FOAM BODIES
    US4224169A (en) * 1978-10-19 1980-09-23 Promotora De Tecnologia Industrial, S.A. Flame retardant compositions and method of preparing same
    FR2489291A1 (en) * 1980-09-03 1982-03-05 Davidovits Joseph MINERAL POLYMERIC COMPOUND AND PROCESS FOR OBTAINING THE SAME
    DE3100626C2 (en) * 1981-01-12 1985-05-15 Schmittmann, Hans-Bernd, Dipl.-Chem. Dr.Rer.Nat., 5620 Velbert Flame-retardant plastics, especially those which can be used as building materials or the like, processes for their production and their use as components
    DE3373465D1 (en) * 1982-12-16 1987-10-15 Dynamit Nobel Ag Water-containing hardenable shaped masses based on inorganic components, and method of producing shaped bodies
    US4521333A (en) * 1983-06-20 1985-06-04 Minnesota Mining And Manufacturing Company Intumescent silicates having improved stability
    DE3633366A1 (en) * 1986-10-01 1988-04-14 Ruetgerswerke Ag METHOD FOR PRODUCING BORSAEURE SUSPENSIONS
    US5036030A (en) * 1989-12-29 1991-07-30 Tokuyama Soda Kabushiki Kaisha Process for preparation of alkaline earth metal aluminosilicate sintered body
    FR2659319B1 (en) * 1990-03-07 1992-07-03 Davidovics Michel PROCESS FOR OBTAINING AN ALUMINO-SILICATE GEOPOLYMER AND PRODUCTS OBTAINED.
    US5342595A (en) * 1990-03-07 1994-08-30 Joseph Davidovits Process for obtaining a geopolymeric alumino-silicate and products thus obtained
    US5156775A (en) * 1991-10-17 1992-10-20 Blount David H Flame retardant compositions
    FR2685913B1 (en) * 1992-01-03 1994-09-23 Poudres & Explosifs Ste Nale MINERAL RESINS AND THEIR PREPARATION PROCESS.

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    DE69410702D1 (en) 1998-07-09
    EP0633231A1 (en) 1995-01-11
    FR2707286B1 (en) 1995-08-18
    FR2707286A1 (en) 1995-01-13

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